Method for preparing a supported catalyst system and its use in a polymerization process

ABSTRACT

The present invention relates to a composition of a carboxylate metal salt in combination with a heated polymerization catalyst to improve the flowability and operability of the catalyst. The invention also relates to methods for preparing the catalyst composition and to its use in a polymerization process.

This application claims the benefit of Provisional application Ser. No.60/256,292, filed Dec. 18, 2000.

FIELD OF THE INVENTION

The present invention relates to a method for preparing a supportedcatalyst system and for its use in a process for polymerizing olefin(s).In particular, the invention is directed to the use of a carboxylatemetal salt that has improved flowability. Specifically, the inventionrelates to a method for preparing a supported catalyst system,especially a bulky ligand metallocene catalyst system, including acarboxylate metal salt that has an improved flowability.

BACKGROUND OF THE INVENTION

Advances in polymerization and catalysis have resulted in the capabilityto produce many new polymers having improved physical and chemicalproperties useful in a wide variety of superior products andapplications. With the development of new catalysts the choice ofpolymerization type (solution, slurry, high pressure or gas phase) forproducing a particular polymer has been greatly expanded. Also, advancesin polymerization technology have provided more efficient, highlyproductive and economically enhanced processes. Especially illustrativeof these advances is the development of technology utilizing bulkyligand metallocene catalyst systems or single site catalyst systems. Inparticular, in a slurry or gas phase process, where typically asupported catalyst system is used, there are a variety of differentmethods described in the art for supporting bulky ligand metallocenecatalyst systems. Regardless of these technological advances in thepolyolefin industry, common problems, as well as new challengesassociated with process operability still exist. For example, thetendency for a gas phase or slurry phase process to foul and/or sheetremains a challenge.

Evidence of, and solutions to, various process operability problems havebeen addressed by many in the art. For example, U.S. Pat. Nos.4,792,592, 4,803,251, 4,855,370 and 5,391,657 all discuss techniques forreducing static generation in a polymerization process by introducing tothe process for example, water, alcohols, ketones, and/or inorganicchemical additives; PCT publication WO 97/14721 published Apr. 24, 1997discusses the suppression of fines that can cause sheeting by adding aninert hydrocarbon to the reactor; U.S. Pat. No. 5,627,243 discusses anew type of distributor plate for use in fluidized bed gas phasereactors; PCT publication WO 96/08520 discusses avoiding theintroduction of a scavenger into the reactor; U.S. Pat. No. 5,461,123discusses using sound waves to reduce sheeting; U.S. Pat. No. 5,066,736and EP-A1 0 549 252 discuss the introduction of an activity retarder tothe reactor to reduce agglomerates; U.S. Pat. No. 5,610,244 relates tofeeding make-up monomer directly into the reactor above the bed to avoidfouling and improve polymer quality; U.S. Pat. No. 5,126,414 discussesincluding an oligomer removal system for reducing distributor platefouling and providing for polymers free of gels; EP-A1 0 453 116published Oct. 23, 1991 discusses the introduction of antistatic agentsto the reactor for reducing the amount of sheets and agglomerates; U.S.Pat. No. 4,012,574 discusses adding a surface-active compound, aperfluorocarbon group, to the reactor to reduce fouling; U.S. Pat. No.5,026,795 discusses the addition of an antistatic agent with a liquidcarrier to the polymerization zone in the reactor; U.S. Pat. No.5,410,002 discusses using a conventional Ziegler-Nattatitanium/magnesium supported catalyst system where a selection ofantistatic agents are added directly to the reactor to reduce fouling;U.S. Pat. Nos. 5,034,480 and 5,034,481 discuss a reaction product of aconventional Ziegler-Natta titanium catalyst with an antistat to produceultrahigh molecular weight ethylene polymers; U.S. Pat. No. 3,082,198discusses introducing an amount of a carboxylic acid dependent on thequantity of water in a process for polymerizing ethylene using atitanium/aluminum organometallic catalysts in a hydrocarbon liquidmedium; and U.S. Pat. No. 3,919,185 describes a slurry process using anonpolar hydrocarbon diluent using a conventional Ziegler-Natta-type orPhillips-type catalyst and a polyvalent metal salt of an organic acidhaving a molecular weight of at least 300.

There are various other known methods for improving operabilityincluding coating the polymerization equipment, for example, treatingthe walls of a reactor using chromium compounds as described in U.S.Pat. Nos. 4,532,311 and 4,876,320; injecting various agents into theprocess, for example PCT Publication WO 97/46599 published Dec. 11, 1997discusses feeding into a lean zone in a polymerization reactor anunsupported, soluble metallocene catalyst system and injectingantifoulants or antistatic agents into the reactor; controlling thepolymerization rate, particularly on start-up; and reconfiguring thereactor design.

Others in the art to improve process operability have discussedmodifying the catalyst system by preparing the catalyst system indifferent ways. For example, methods in the art include combining thecatalyst system components in a particular order; manipulating the ratioof the various catalyst system components; varying the contact timeand/or temperature when combining the components of a catalyst system;or simply adding various compounds to the catalyst system. Especiallyillustrative in the art is the preparation procedures and methods forproducing bulky ligand metallocene catalyst systems, more particularlysupported bulky ligand metallocene catalyst systems with reducedtendencies for fouling and better operability. Examples of theseinclude: WO 96/11961 published Apr. 26, 1996 discusses as a component ofa supported catalyst system an antistatic agent for reducing fouling andsheeting in a gas, slurry or liquid pool polymerization process; U.S.Pat. No. 5,283,278 is directed towards the prepolymerization of ametallocene catalyst or a conventional Ziegler-Natta catalyst in thepresence of an antistatic agent; U.S. Pat. Nos. 5,332,706 and 5,473,028have resorted to a particular technique for forming a catalyst byincipient impregnation; U.S. Pat. Nos. 5,427,991 and 5,643,847 describethe chemical bonding of non-coordinating anionic activators to supports;U.S. Pat. No. 5,492,975 discusses polymer bound metallocene catalystsystems; U.S. Pat. No. 5,661,095 discusses supporting a metallocenecatalyst on a copolymer of an olefin and an unsaturated silane; PCTpublication WO 97/06186 published Feb. 20, 1997 teaches removinginorganic and organic impurities after formation of the metallocenecatalyst itself; PCT publication WO 97/15602 published May 1, 1997discusses readily supportable metal complexes; PCT publication WO97/27224 published Jul. 31, 1997 relates to forming a supportedtransition metal compound in the presence of an unsaturated organiccompound having at least one terminal double bond; and EP-A2-811 638discusses using a metallocene catalyst and an activating cocatalyst in apolymerization process in the presence of a nitrogen containingantistatic agent.

While all these possible solutions might reduce the level of fouling orsheeting somewhat, some are expensive to employ and/or may not reducefouling and sheeting to a level sufficient to successfully operate acontinuous process, particularly a commercial or large-scale process.

Applicants discovered that using a carboxylate metal salt in conjunctionwith a supported catalyst system, preferably a bulky ligand metallocenecatalyst system, more preferably a supported bulky ligand metallocenecatalyst system, substantially improves process operability. See forexample U.S. patent application Ser. No. 09/397,409, filed Sep. 16, 1999and U.S. patent application Ser. No. 09/397,410, filed Sep. 16, 1999,which are both herein fully incorporated by reference. However, as aresult of using this combination, the improved supported catalystcomposition becomes somewhat more difficult to feed to a reactor. Thesupported catalyst becomes sticky or statically inclined, thuspreventing its continuous and smooth introduction into the reactor.

Thus, it would be advantageous to have an improved catalyst compositionthat flows more easily and is capable of operating in a polymerizationprocess continuously with enhanced reactor operability.

SUMMARY OF THE INVENTION

This invention provides a method of making a new and improved flowingsupported catalyst system, particularly a supported bulky ligandmetallocene catalyst system, that contains a carboxylate metal salt, andfor the catalyst systems use in a polymerizing process.

The invention also provides for a catalyst composition of a catalystsystem and a carboxylate metal salt that is useful in a polymerizationprocess. In one embodiment, the carboxylate metal salt is present in thecomposition in an amount greater than 3.5 weight percent based on thetotal weight of the catalyst composition. In one embodiment, the methodof the invention comprises the step of combining, contacting, blendingand/or mixing a catalyst system, preferably a supported catalyst system,with a carboxylate metal salt wherein the catalyst system is heated to atemperature above room temperature, preferably above 30° C. In oneembodiment the catalyst system comprises a conventional-type transitionmetal catalyst compound. In the most preferred embodiment the catalystsystem comprises a bulky ligand metallocene catalyst compound. Thecombination of the heated catalyst system and the carboxylate metal saltis useful in any olefin polymerization process. The preferredpolymerization processes are a gas phase or a slurry phase process, mostpreferably a gas phase process.

In an embodiment, the invention provides for a method of making acatalyst composition useful for the polymerization of olefin(s), themethod including combining, contacting, blending and/or mixing apolymerization catalyst with at least one carboxylate metal salt whereinthe polymerization catalyst is heated to a temperature above roomtemperature, preferably greater than 30° C., prior to being contactedwith the carboxylate metal salt. In an embodiment, the polymerizationcatalyst is a conventional-type transition metal polymerizationcatalyst, more preferably a supported conventional-type transition metalpolymerization catalyst. In the most preferred embodiment, thepolymerization catalyst is a bulky ligand metallocene catalyst, mostpreferably a supported bulky ligand metallocene polymerization catalyst.

In one preferred embodiment, the invention is directed to a catalystcomposition comprising a catalyst compound, preferably aconventional-type transition metal catalyst compound, more preferably abulky ligand metallocene catalyst compound, an activator and/orcocatalyst, a carrier, and a carboxylate metal salt. In this embodiment,the catalyst compound, the activator and the carrier are heated to atemperature above room temperature, preferably greater than 30° C.Further, in this embodiment, it is preferred that the carboxylate metalsalt is present in an amount greater than 3.5 weight percent based onthe total weight based on the total weight of the catalyst compound.

In yet another embodiment, the invention relates to a process forpolymerizing olefin(s) in the presence of a catalyst compositioncomprising a polymerization catalyst and a carboxylate metal salt,wherein the polymerization catalyst is heated to a temperature greaterthan room temperature, preferably greater than 30° C., prior tocontacting or combining with the carboxylate metal salt, preferably thepolymerization catalyst comprises a carrier, more preferably thepolymerization catalyst comprises one or more of combination of aconventional-type catalyst compound and/or a bulky ligand metallocenecatalyst compound.

In a preferred method for making the catalyst composition of theinvention, the method comprises the steps of combining a bulky ligandmetallocene catalyst compound, an activator and a carrier to form asupported bulky ligand metallocene catalyst system, heating thesupported bulky ligand metallocene catalyst system to a temperaturegreater than room temperature, preferably greater than 30° C.,contacting the supported bulky ligand metallocene catalyst compound acarboxylate metal salt. In the most preferred embodiment, the supportedbulky ligand metallocene catalyst system and the carboxylate metal saltare in a substantially dry state or dried state.

In an embodiment, the invention provides for a process for polymerizingolefin(s) in the presence of a polymerization catalyst that has beenheated to a temperature greater than room temperature, preferablygreater than 30° C., prior to being combined, contacted, blended, ormixed with at least one carboxylate metal salt.

DETAILED DESCRIPTION OF THE INVENTION

Introduction

The invention is directed toward a method for making a supportedcatalyst system. It has been suprisingly discovered that combining apre-heated supported catalyst, preferably a bulky ligand metallocenecatalyst system, with a carboxylate metal salt, results in a supportedcatalyst system with improved flowability and operability. Carboxylatemetal salts are difficult to handle, particularly, because of their poormorphology, low bulk density, and fluffy consistency. Therefore,combining the carboxylate metal salt with a supported catalyst system isa challenge. Increasing the amount of carboxylate metal salt used with apolymerization catalyst, requires extended mixing times, resulting in adecrease in catalyst flow. Furthermore, increasing the amount ofcarboxylate metal salt used with a supported catalyst system can effectcatalyst activity. However, combining a carboxylate metal salt with aheated or hot supported catalyst results in a catalyst compositioncontaining more carboxylate metal salt, without a decrease in catalystactivity.

Conventional Transition Metal Catalysts

Conventional transition metal catalysts are those traditionalZiegler-Natta catalysts and Phillips-type chromium catalyst well knownin the art. Examples of conventional transition metal catalysts arediscussed in U.S. Pat. Nos. 4,115,639, 4,077,904 4,482,687, 4,564,605,4,721,763, 4,879,359 and 4,960,741 all of which are herein fullyincorporated by reference. The conventional transition metal catalystcompounds that may be used in the present invention include transitionmetal compounds from Groups III to VIII, preferably IVB to VIB of thePeriodic Table of Elements.

These conventional transition metal catalysts may be represented by theformula: MR_(x), where M is a metal from Groups IIIB to VIII, preferablyGroup IVB, more preferably titanium; R is a halogen or a hydrocarbyloxygroup; and x is the valence of the metal M. Non-limiting examples of Rinclude alkoxy, phenoxy, bromide, chloride and fluoride. Non-limitingexamples of conventional transition metal catalysts where M is titaniuminclude TiCl₄, TiBr₄, Ti(OC₂H₅)₃Cl, Ti(OC₂H₅)Cl₃, Ti(OC₄H₉)₃Cl,Ti(OC₃H₇)₂Cl₂, Ti(OC₂H₅)₂Br₂, TiCl₃.1/3AlCl₃ and Ti(OC₁₂H₂₅)Cl₃.

Conventional-type transition metal catalyst compounds based onmagnesium/titanium electron-donor complexes that are useful in theinvention are described in, for example, U.S. Pat. Nos. 4,302,565 and4,302,566, which are herein fully incorporate by reference. TheMgTiCl₆(ethyl acetate)₄ derivative is particularly preferred. BritishPatent Application 2,105,355, herein incorporated by reference,describes various conventional-type vanadium catalyst compound.

Conventional chromium catalyst compounds, often referred to asPhillips-type catalysts, suitable for use in the present inventioninclude CrO₃, chromocene, silyl chromate, chromyl chloride (CrO₂Cl₂),chromium-2-ethyl-hexanoate, chromium acetylacetonate (Cr(AcAc)₃), andthe like. Non-limiting examples are disclosed in U.S. Pat. Nos.2,285,721, 3,242,099 and 3,231,550, which are herein fully incorporatedby reference.

Still other conventional transition metal catalyst compounds andcatalyst systems suitable for use in the present invention are disclosedin U.S. Pat. Nos. 4,124,532, 4,302,565, 4,302,566 and 5,763,723 andpublished EP-A2 0 416 815 A2 and EP-A1 0 420 436, which are all hereinincorporated by reference.

Other catalysts may include cationic catalysts such as AlCl₃, and othercobalt and iron catalysts well known in the art.

Typically, these conventional transition metal catalyst compoundsexcluding some conventional chromium catalyst compounds are activatedwith one or more of the conventional cocatalysts described below.

Conventional Cocatalysts

Conventional cocatalyst compounds for the above conventional transitionmetal catalyst compounds may be represented by the formula M³M⁴ _(v)X²_(c)R³ _(b-c), wherein M³ is a metal from Group IA, IIA, IIB and IIIA ofthe Periodic Table of Elements; M⁴ is a metal of Group IA of thePeriodic Table of Elements; v is a number from 0 to 1; each X² is anyhalogen; c is a number from 0 to 3; each R³ is a monovalent hydrocarbonradical or hydrogen; b is a number from 1 to 4; and wherein b minus c isat least 1. Other conventional-type organometallic cocatalyst compoundsfor the above conventional-type transition metal catalysts have theformula M³R³ _(k), where M³ is a Group IA, IIA, IIB or IIIA metal, suchas lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium,and gallium; k equals 1, 2 or 3 depending upon the valency of M³ whichvalency in turn normally depends upon the particular Group to which M³belongs; and each R³ may be any monovalent hydrocarbon radical.

Non-limiting examples of conventional-type organometallic cocatalystcompounds of Group IA, IIA, IIB and IIIA useful with theconventional-type catalyst compounds described above includemethyllithium, butyllithium, dihexylmercury, butylmagnesium,diethylcadmium, benzylpotassium, diethylzinc, tri-n-butylaluminum,diisobutyl ethylboron, diethylcadmium, di-n-butylzinc andtri-n-amylboron, and, in particular, the aluminum alkyls, such astri-hexyl-aluminum, triethylaluminum, trimethylaluminum, andtri-isobutylaluminum. Other conventional-type cocatalyst compoundsinclude mono-organohalides and hydrides of Group IIA metals, and mono-or di-organohalides and hydrides of Group IIIA metals. Non-limitingexamples of such conventional-type cocatalyst compounds includedi-isobutylaluminum bromide, isobutylboron dichloride, methyl magnesiumchloride, ethylberyllium chloride, ethylcalcium bromide,di-isobutylaluminum hydride, methylcadmium hydride, diethylboronhydride, hexylberyllium hydride, dipropylboron hydride, octylmagnesiumhydride, butylzinc hydride, dichloroboron hydride, di-bromo-aluminumhydride and bromocadmium hydride. Conventional-type organometalliccocatalyst compounds are known to those in the art and a more completediscussion of these compounds may be found in U.S. Pat. Nos. 3,221,002and 5,093,415, which are herein fully incorporated by reference.

For purposes of this patent specification and appended claimsconventional transition metal catalyst compounds exclude those bulkyligand metallocene catalyst compounds discussed below.

Bulky Ligand Metallocene Catalyst Compounds

Generally, bulky ligand metallocene catalyst compounds include half andfull sandwich compounds having one or more bulky ligands bonded to atleast one metal atom. Typical bulky ligand metallocene compounds aregenerally described as containing one or more bulky ligand(s) and one ormore leaving group(s) bonded to at least one metal atom. In onepreferred embodiment, at least one bulky ligand is η-bonded to the metalatom, most preferably η⁵-bonded to the metal atom.

The bulky ligands are generally represented by one or more open,acyclic, or fused ring(s) or ring system(s) or a combination thereof.These bulky ligands, preferably the ring(s) or ring system(s) aretypically composed of atoms selected from Groups 13 to 16 atoms of thePeriodic Table of Elements, preferably the atoms are selected from thegroup consisting of carbon, nitrogen, oxygen, silicon, sulfur,phosphorous, germanium, boron and aluminum or a combination thereof.Most preferably the ring(s) or ring system(s) are composed of carbonatoms such as but not limited to those cyclopentadienyl ligands orcyclopentadienyl-type ligand structures or other similar functioningligand structure such as a pentadiene, a cyclooctatetraendiyl or animide ligand. The metal atom is preferably selected from Groups 3through 15 and the lanthanide or actinide series of the Periodic Tableof Elements. Preferably the metal is a transition metal from Groups 4through 12, more preferably Groups 4, 5 and 6, and most preferably thetransition metal is from Group 4.

In one embodiment, the bulky ligand metallocene catalyst compounds ofthe invention are represented by the formula:

L^(A)L^(B)MQ_(n)  (I)

where M is a metal atom from the Periodic Table of the Elements and maybe a Group 3 to 12 metal or from the lanthanide or actinide series ofthe Periodic Table of Elements, preferably M is a Group 4, 5 or 6transition metal, more preferably M is a Group 4 transition metal, evenmore preferably M is zirconium, hafnium or titanium. The bulky ligands,L^(A) and L^(B), are open, acyclic or fused ring(s) or ring system(s)and are any ancillary ligand system, including unsubstituted orsubstituted, cyclopentadienyl ligands or cyclopentadienyl-type ligands,heteroatom substituted and/or heteroatom containingcyclopentadienyl-type ligands. Non-limiting examples of bulky ligandsinclude cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands,indenyl ligands, benzindenyl ligands, fluorenyl ligands,octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,cyclopentacyclododecene ligands, azenyl ligands, azulene ligands,pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125),pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzeneligands and the like, including hydrogenated versions thereof, forexample tetrahydroindenyl ligands. In one embodiment, L^(A) and L^(B)may be any other ligand structure capable of η-bonding to M, preferablyη³-bonding to M and most preferably η⁵-bonding. In yet anotherembodiment, the atomic molecular weight (MW) of L^(A) or L^(B) exceeds60 a.m.u., preferably greater than 65 a.m.u. In another embodiment,L^(A) and L^(B) may comprise one or more heteroatoms, for example,nitrogen, silicon, boron, germanium, sulfur and phosphorous, incombination with carbon atoms to form an open, acyclic, or preferably afused, ring or ring system, for example, a hetero-cyclopentadienylancillary ligand. Other L^(A) and L^(B) bulky ligands include but arenot limited to bulky amides, phosphides, alkoxides, aryloxides, imides,carbolides, borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Independently, each L^(A) and L^(B) may be the sameor different type of bulky ligand that is bonded to M. In one embodimentof formula (I) only one of either L^(A) or L^(B) is present.

Independently, each L^(A) and L^(B) may be unsubstituted or substitutedwith a combination of substituent groups R. Non-limiting examples ofsubstituent groups R include one or more from the group selected fromhydrogen, or linear, branched alkyl radicals, or alkenyl radicals,alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals,aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals,dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonylradicals, carbomoyl radicals, alkyl- or dialkyl-carbamoyl radicals,acyloxy radicals, acylamino radicals, aroylamino radicals, straight,branched or cyclic, alkylene radicals, or combination thereof. In apreferred embodiment, substituent groups R have up to 50 non-hydrogenatoms, preferably from 1 to 30 carbon, that can also be substituted withhalogens or heteroatoms or the like. Non-limiting examples of alkylsubstituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl,cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, includingall their isomers, for example tertiary butyl, isopropyl, and the like.Other hydrocarbyl radicals include fluoromethyl, fluroethyl,difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbylsubstituted organometalloid radicals including trimethylsilyl,trimethylgermyl, methyldiethylsilyl and the like; andhalocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstitiuted boronradicals including dimethylboron for example; and disubstitutedpnictogen radicals including dimethylamine, dimethylphosphine,diphenylamine, methylphenylphosphine, chalcogen radicals includingmethoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.Non-hydrogen substituents R include the atoms carbon, silicon, boron,aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and thelike, including olefins such as but not limited to olefinicallyunsaturated substituents including vinyl-terminated ligands, for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two Rgroups, preferably two adjacent R groups, are joined to form a ringstructure having from 3 to 30 atoms selected from carbon, nitrogen,oxygen, phosphorous, silicon, germanium, aluminum, boron or acombination thereof. Also, a substituent group R group such as 1-butanylmay form a carbon sigma bond to the metal M.

Other ligands may be bonded to the metal M, such as at least one leavinggroup Q. For the purposes of this patent specification and appendedclaims the term “leaving group” is any ligand that can be abstractedfrom a bulky ligand metallocene catalyst compound to form a bulky ligandmetallocene catalyst cation capable of polymerizing one or moreolefin(s). In one embodiment, Q is a monoanionic labile ligand having asigma-bond to M. Depending on the oxidation state of the metal, thevalue for n is 0, 1 or 2 such that formula (I) above represents aneutral bulky ligand metallocene catalyst compound.

Non-limiting examples of Q ligands include weak bases such as amines,phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals havingfrom 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof. In another embodiment, two or more Q's form a partof a fused ring or ring system. Other examples of Q ligands includethose substituents for R as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike.

In one embodiment, the bulky ligand metallocene catalyst compounds ofthe invention include those of formula (I) where L^(A) and L^(B) arebridged to each other by at least one bridging group, A, such that theformula is represented by

L^(A)AL^(B)MQ_(n)  (II)

These bridged compounds represented by formula (II) are known asbridged, bulky ligand metallocene catalyst compounds. L^(A), L^(B), M, Qand n are as defined above. Non-limiting examples of bridging group Ainclude bridging groups containing at least one Group 13 to 16 atom,often referred to as a divalent moiety such as but not limited to atleast one of a carbon, oxygen, nitrogen, silicon, aluminum, boron,germanium and tin atom or a combination thereof. Preferably bridginggroup A contains a carbon, silicon or germanium atom, most preferably Acontains at least one silicon atom or at least one carbon atom. Thebridging group A may also contain substituent groups R as defined aboveincluding halogens and iron. Non-limiting examples of bridging group Amay be represented by R′₂C, R′₂Si, R′₂Si R′₂Si, R′₂Ge, R′P, where R′ isindependently, a radical group which is hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl,hydrocarbyl-substituted organometalloid, halocarbyl-substitutedorganometalloid, disubstituted boron, disubstituted pnictogen,substituted chalcogen, or halogen or two or more R′ may be joined toform a ring or ring system. In one embodiment, the bridged, bulky ligandmetallocene catalyst compounds of formula (II) have two or more bridginggroups A (EP 664 301 B1).

In one embodiment, the bulky ligand metallocene catalyst compounds arethose where the R substituents on the bulky ligands L^(A) and L^(B) offormulas (I) and (II) are substituted with the same or different numberof substituents on each of the bulky ligands. In another embodiment, thebulky ligands L^(A) and L^(B) of formulas (I) and (II) are differentfrom each other.

Other bulky ligand metallocene catalyst compounds and catalyst systemsuseful in the invention may include those described in U.S. Pat. Nos.5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022, 5,276,208,5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401, 5,723,398,5,753,578, 5,854,363, 5,856,547 5,858,903, 5,859,158, 5,900,517,5,939,503 and 5,962,718 and PCT publications WO 93/08221, WO 93/08199,WO 95/07140, WO 98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO99/02540 and WO 99/14221 and European publications EP-A-0 578 838,EP-A-0 638 595, EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834,EP-B1-0 632 819, EP-B1-0 739 361, EP-B1-0 748 821 and EP-B1-0 757 996,all of which are herein fully incorporated by reference.

In one embodiment, bulky ligand metallocene catalysts compounds usefulin the invention include bridged heteroatom, mono-bulky ligandmetallocene compounds. These types of catalysts and catalyst systems aredescribed in, for example, PCT publication WO 92/00333, WO 94/07928, WO91/04257, WO 94/03506, WO96/00244, WO 97/15602 and WO 99/20637 and U.S.Pat. Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and5,264,405 and European publication EP-A-0 420 436, all of which areherein fully incorporated by reference.

In this embodiment, the bulky ligand metallocene catalyst compound isrepresented by the formula:

L^(C)AJMQ_(n)  (III)

where M is a Group 3 to 16 metal atom or a metal selected from the Groupof actinides and lanthanides of the Periodic Table of Elements,preferably M is a Group 4 to 12 transition metal, and more preferably Mis a Group 4, 5 or 6 transition metal, and most preferably M is a Group4 transition metal in any oxidation state, especially titanium; L^(C) isa substituted or unsubstituted bulky ligand bonded to M; J is bonded toM; A is bonded to L^(C) and J; J is a heteroatom ancillary ligand; and Ais a bridging group; Q is a univalent anionic ligand; and n is theinteger 0, 1 or 2. In formula (III) above, L^(C), A and J form a fusedring system. In an embodiment, L^(C) of formula (III) is as definedabove for L^(A), A, M and Q of formula (III) are as defined above informula (I).

In formula (III) J is a heteroatom containing ligand in which J is anelement with a coordination number of three from Group 15 or an elementwith a coordination number of two from Group 16 of the Periodic Table ofElements. Preferably J contains a nitrogen, phosphorus, oxygen or sulfuratom with nitrogen being most preferred.

In another embodiment, the bulky ligand type metallocene catalystcompound is a complex of a metal, preferably a transition metal, a bulkyligand, preferably a substituted or unsubstituted pi-bonded ligand, andone or more heteroallyl moieties, such as those described in U.S. Pat.Nos. 5,527,752 and 5,747,406 and EP-B1-0 735 057, all of which areherein fully incorporated by reference.

In an embodiment, the bulky ligand metallocene catalyst compound isrepresented by the formula:

L^(D)MQ₂(YZ)X_(n)  (IV)

where M is a Group 3 to 16 metal, preferably a Group 4 to 12 transitionmetal, and most preferably a Group 4, 5 or 6 transition metal; L^(D) isa bulky ligand that is bonded to M; each Q is independently bonded to Mand Q₂(YZ) forms a unicharged polydentate ligand; A or Q is a univalentanionic ligand also bonded to M; X is a univalent anionic group when nis 2 or X is a divalent anionic group when n is 1; n is 1 or 2.

In formula (IV), L and M are as defined above for formula (I). Q is asdefined above for formula (I), preferably Q is selected from the groupconsisting of —O—, —NR—, —CR₂— and —S—; Y is either C or S; Z isselected from the group consisting of —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂,—H, and substituted or unsubstituted aryl groups, with the proviso thatwhen Q is —NR— then Z is selected from one of the group consisting of—OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 to 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

In another embodiment of the invention, the bulky ligandmetallocene-type catalyst compounds are heterocyclic ligand complexeswhere the bulky ligands, the ring(s) or ring system(s), include one ormore heteroatoms or a combination thereof. Non-limiting examples ofheteroatoms include a Group 13 to 16 element, preferably nitrogen,boron, sulfur, oxygen, aluminum, silicon, phosphorous and tin. Examplesof these bulky ligand metallocene catalyst compounds are described in WO96/33202, WO 96/34021, WO 97/17379, WO 98/22486 and WO 99/40095(dicarbamoyl metal complexes) and EP-A1-0 874 005 and U.S. Pat. Nos.5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417, and5,856,258 all of which are herein incorporated by reference.

In another embodiment, the bulky ligand metallocene catalyst compoundsare those complexes known as transition metal catalysts based onbidentate ligands containing pyridine or quinoline moieties, such asthose described in U.S. application Ser. No. 09/103,620 filed Jun. 23,1998, which is herein incorporated by reference. In another embodiment,the bulky ligand metallocene catalyst compounds are those described inPCT publications WO 99/01481 and WO 98/42664, which are fullyincorporated herein by reference.

In one embodiment, the bulky ligand metallocene catalyst compound isrepresented by the formula:

((Z)XA_(t)(YJ))_(q)MQ_(n)  (V)

where M is a metal selected from Group 3 to 13 or lanthanide andactinide series of the Periodic Table of Elements; Q is bonded to M andeach Q is a monovalent, bivalent, or trivalent anion; X and Y are bondedto M; one or more of X and Y are heteroatoms, preferably both X and Yare heteroatoms; Y is contained in a heterocyclic ring J, where Jcomprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbonatoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms,preferably 1 to 50 carbon atoms, preferably Z is a cyclic groupcontaining 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1;when t is 1, A is a bridging group joined to at least one of X, Y or J,preferably X and J; q is 1 or 2; n is an integer from 1 to 4 dependingon the oxidation state of M. In one embodiment, where X is oxygen orsulfur then Z is optional. In another embodiment, where X is nitrogen orphosphorous then Z is present. In an embodiment, Z is preferably an arylgroup, more preferably a substituted aryl group.

Other Bulky Ligand Metallocene Catalyst Compounds

It is within the scope of this invention, in one embodiment, that thebulky ligand metallocene catalyst compounds include complexes of Ni²⁺and Pd²⁺ described in the articles Johnson, et al., “New Pd(II)- andNi(II)-Based Catalysts for Polymerization of Ethylene and a-Olefins”, J.Am. Chem. Soc. 1995, 117, 6414-6415 and Johnson, et al.,“Copolymerization of Ethylene and Propylene with Functionalized VinylMonomers by Palladium(II) Catalysts”, J. Am. Chem. Soc., 1996, 118,267-268, and WO 96/23010 published Aug. 1, 1996, WO 99/02472, U.S. Pat.Nos. 5,852,145, 5,866,663 and 5,880,241, which are all herein fullyincorporated by reference. These complexes can be either dialkyl etheradducts, or alkylated reaction products of the described dihalidecomplexes that can be activated to a cationic state by the activators ofthis invention described below.

Also included as bulky ligand metallocene catalyst are those diiminebased ligands of Group 8 to 10 metal compounds disclosed in PCTpublications WO 96/23010 and WO 97/48735 and Gibson, et. al., Chem.Comm., pp. 849-850 (1998), all of which are herein incorporated byreference.

Other bulky ligand metallocene catalysts are those Group 5 and 6 metalimido complexes described in EP-A2-0 816 384 and U.S. Pat. No.5,851,945, which is incorporated herein by reference. In addition, bulkyligand metallocene catalysts include bridged bis(arylamido) Group 4compounds described by D. H. McConville, et al., in Organometallics1195, 14, 5478-5480, which is herein incorporated by reference. Inaddition, bridged bis(amido) catalyst compounds are described in WO96/27439, which is herein incorporated by reference. Other bulky ligandmetallocene catalysts are described as bis(hydroxy aromatic nitrogenligands) in U.S. Pat. No. 5,852,146, which is incorporated herein byreference. Other metallocene catalysts containing one or more Group 15atoms include those described in WO 98/46651, which is hereinincorporated herein by reference. Still another metallocene bulky ligandmetallocene catalysts include those multinuclear bulky ligandmetallocene catalysts as described in WO 99/20665, which is incorporatedherein by reference.

It is also contemplated that in one embodiment, the bulky ligandmetallocene catalysts of the invention described above include theirstructural or optical or enantiomeric isomers (meso and racemic isomers,for example see U.S. Pat. No. 5,852,143, incorporated herein byreference) and mixtures thereof.

Activator and Activation Methods for the Bulky Ligand MetalloceneCatalyst Compounds

The above described bulky ligand metallocene catalyst compounds aretypically activated in various ways to yield catalyst compounds having avacant coordination site that will coordinate, insert, and polymerizeolefin(s).

For the purposes of this patent specification and appended claims, theterm “activator” is defined to be any compound or component or methodwhich can activate any of the bulky ligand metallocene catalystcompounds or other catalyst compounds of the invention as describedabove. Non-limiting activators, for example may include a Lewis acid ora non-coordinating ionic activator or ionizing activator or any othercompound including Lewis bases, aluminum alkyls, conventional-typecocatalysts and combinations thereof that can convert a neutral bulkyligand metallocene catalyst compound to a catalytically active bulkyligand metallocene cation. It is within the scope of this invention touse alumoxane or modified alumoxane as an activator, and/or to also useionizing activators, neutral or ionic, such as tri (n-butyl) ammoniumtetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boronmetalloid precursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983) or combinationthereof, that would ionize the neutral bulky ligand metallocene catalystcompound.

In one embodiment, an activation method using ionizing ionic compoundsnot containing an active proton but capable of producing both a bulkyligand metallocene catalyst cation and a non-coordinating anion are alsocontemplated, and are described in EP-A-0 426 637, EP-A-0 573 403 andU.S. Pat. No. 5,387,568, which are all herein incorporated by reference.

There are a variety of methods for preparing alumoxane and modifiedalumoxanes, non-limiting examples of which are described in U.S. Pat.Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734,4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801,5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838,5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166, 5,856,256 and5,939,346 and European publications EP-A-0 561 476, EP-B1-0 279 586,EP-A-0 594-218 and EP-B1-0 586 665, and PCT publication WO 94/10180, allof which are herein fully incorporated by reference.

Organoaluminum compounds useful as activators include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum and the like.

Ionizing compounds may contain an active proton, or some other cationassociated with but not coordinated to or only loosely coordinated tothe remaining ion of the ionizing compound. Such compounds and the likeare described in European publications EP-A-0 570 982, EP-A-0 520 732,EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, andU.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025,5,384,299 and 5,502,124 and U.S. patent application Ser. No. 08/285,380,filed Aug. 3, 1994, all of which are herein fully incorporated byreference.

Other activators include those described in PCT publication WO 98/07515such as tris (2,2′,2″-nonafluorobiphenyl) fluoroaluminate, whichpublication is fully incorporated herein by reference. Combinations ofactivators are also contemplated by the invention, for example,alumoxanes and ionizing activators in combinations, see for example,EP-B1 0 573 120, PCT publications WO 94/07928 and WO 95/14044 and U.S.Pat. Nos. 5,153,157 and 5,453,410 all of which are herein fullyincorporated by reference. WO 98/09996 incorporated herein by referencedescribes activating bulky ligand metallocene catalyst compounds withperchlorates, periodates and iodates including their hydrates. WO98/30602 and WO 98/30603 incorporated by reference describe the use oflithium (2,2′-bisphenyl-ditrimethylsilicate)•4THF as an activator for abulky ligand metallocene catalyst compound. WO 99/18135 incorporatedherein by reference describes the use of organo-boron-aluminumactivators. EP-B1-0 781 299 describes using a silylium salt incombination with a non-coordinating compatible anion. Also, methods ofactivation such as using radiation (see EP-B1-0 615 981 hereinincorporated by reference), electro-chemical oxidation, and the like arealso contemplated as activating methods for the purposes of renderingthe neutral bulky ligand metallocene catalyst compound or precursor to abulky ligand metallocene cation capable of polymerizing olefins. Otheractivators or methods for activating a bulky ligand metallocene catalystcompound are described in for example, U.S. Pat. Nos. 5,849,852,5,859,653 and 5,869,723 and WO 98/32775, WO 99/42467(dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazolide),which are herein incorporated by reference

It is also within the scope of this invention that one or more of theabove described bulky ligand metallocene catalyst compounds orconventional catalyst compounds can be combined with one or moreactivators or activation methods described above.

It is further contemplated by the invention that other catalysts can becombined with the bulky ligand metallocene catalyst compounds of theinvention. For example, see U.S. Pat. Nos. 4,937,299, 4,935,474,5,281,679, 5,359,015, 5,470,811, and 5,719,241 all of which are hereinfully incorporated herein reference. It is also contemplated that anyone of the bulky ligand metallocene catalyst compounds of the inventionhave at least one fluoride or fluorine containing leaving group asdescribed in U.S. application Ser. No. 09/191,916 filed Nov. 13, 1998.

In another embodiment of the invention one or more bulky ligandmetallocene catalyst compounds or catalyst systems may be used incombination with one or more conventional-type catalyst compounds orcatalyst systems. Non-limiting examples of mixed catalysts and catalystsystems are described in U.S. Pat. Nos. 4,159,965, 4,325,837, 4,701,432,5,124,418, 5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264,5,723,399 and 5,767,031 and PCT Publication WO 96/23010 published Aug.1, 1996, all of which are herein fully incorporated by reference.

Carboxylate Metal Salt

Carboxylate metal salts are well known in the art as additives for usewith polyolefins, for example as a film processing aid. These types ofpost reactor processing additives are commonly used as emulsifyingagents, antistat and antifogging agents, stabilizers, foaming aids,lubrication aids, mold release agents, nucleating agents, and slip andantiblock agents and the like. Thus, it was truly unexpected that thesepost reactor agents or aids would be useful with a polymerizationcatalyst to improve the operability of a polymerization process.

For the purposes of this patent specification and appended claims theterm “carboxylate metal salt” is any mono- or di- or tri-carboxylic acidsalt with a metal portion from the Periodic Table of Elements.Non-limiting examples include saturated, unsaturated, aliphatic,aromatic or saturated cyclic carboxylic acid salts where the carboxylateligand has preferably from 2 to 24 carbon atoms, such as acetate,propionate, butyrate, valerate, pivalate, caproate, isobuytlacetate,t-butyl-acetate, caprylate, heptanate, pelargonate, undecanoate, oleate,octoate, palmitate, myristate, margarate, stearate, arachate andtercosanoate. Non-limiting examples of the metal portion includes ametal from the Periodic Table of Elements selected from the group of Al,Mg, Ca, Sr, Sn, Ti, V, Ba, Zn, Cd, Hg, Mn, Fe, Co, Ni, Pd, Li and Na.

In one embodiment, the carboxylate metal salt is represented by thefollowing general formula:

M(Q)_(X)(OOCR)_(Y)

where M is a metal from Groups 1 to 16 and the Lanthanide and Actinideseries, preferably from Groups 1 to 7 and 13 to 16, more preferably fromGroups 3 to 7 and 13 to 16, even more preferably Groups 2 and 13, andmost preferably Group 13; Q is halogen, hydrogen, a hydroxy orhydroxide, alkyl, alkoxy, aryloxy, siloxy, silane sulfonate group orsiloxane; R is a hydrocarbyl radical having from 2 to 100 carbon atoms,preferably 4 to 50 carbon atoms; and x is an integer from 0 to 3 and yis an integer from 1 to 4 and the sum of x and y is equal to the valenceof the metal. In a preferred embodiment of the above formula y is aninteger from 1 to 3, preferably 1 to 2, especially where M is a Group 13metal.

Non-limiting examples of R in the above formula include hydrocarbylradicals having 2 to 100 carbon atoms that include alkyl, aryl,aromatic, aliphatic, cyclic, saturated or unsaturated hydrocarbylradicals. In an embodiment of the invention, R is a hydrocarbyl radicalhaving greater than or equal to 8 carbon atoms, preferably greater thanor equal to 12 carbon atoms and more preferably greater than or equal to17 carbon atoms. In another embodiment R is a hydrocarbyl radical havingfrom 17 to 90 carbon atoms, preferably 17 to 72, and most preferablyfrom 17 to 54 carbon atoms.

Non-limiting examples of Q in the above formula include one or more,same or different, hydrocarbon containing group such as alkyl,cycloalkyl, aryl, alkenyl, arylalkyl, arylalkenyl or alkylaryl,alkylsilane, arylsilane, alkylamine, arylamine, alkyl phosphide, alkoxyhaving from 1 to 30 carbon atoms. The hydrocarbon containing group maybe linear, branched, or even substituted. Also, Q in one embodiment isan inorganic group such as a halide, sulfate or phosphate

In one embodiment, the more preferred carboxylate metal salts are thosealuminum carboxylates such as aluminum mono, di- and tri-stearates,aluminum octoates, oleates and cyclohexylbutyrates. In yet a morepreferred embodiment, the carboxylate metal salt is (CH₃(CH₂)₁₆COO)₃Al,a aluminum tri-stearate (preferred melting point 115° C.),(CH₃(CH₂)₁₆COO)₂—Al—OH, a aluminum di-stearate (preferred melting point145° C.), and a CH₃(CH₂)₁₆COO—Al(OH)₂, an aluminum mono-stearate(preferred melting point 155° C.).

Non-limiting commercially available carboxylate metal salts for exampleinclude Witco Aluminum Stearate # 18, Witco Aluminum Stearate # 22,Witco Aluminum Stearate # 132 and Witco Aluminum Stearate EA Food Grade,all of which are available from Witco Corporation, Memphis, Tenn.

In one embodiment the carboxylate metal salt has a melting point fromabout 30° C. to about 250° C., more preferably from about 37° C. toabout 220° C., even more preferably from about 50° C. to about 200° C.,and most preferably from about 100° C. to about 200° C. In a mostpreferred embodiment, the carboxylate metal salt is an aluminum stearatehaving a melting point in the range of from about 135° C. to about 165°C.

In another preferred embodiment the carboxylate metal salt has a meltingpoint greater than the polymerization temperature in the reactor.

Other examples of carboxylate metal salts include titanium stearates,tin stearates, calcium stearates, zinc stearates, boron stearate andstrontium stearates.

The carboxylate metal salt in one embodiment may be combined withantistatic agents such as fatty amines, for example, Kemamine AS 990/2zinc additive, a blend of ethoxylated stearyl amine and zinc stearate,or Kemamine AS 990/3, a blend of ethoxylated stearyl amine, zincstearate and octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate. Boththese blends are available from Witco Corporation, Memphis, Tenn.

Supports, Carriers and General Supporting Techniques

The above described catalyst compounds, particularly the bulky ligandmetallocene catalyst compounds and catalyst systems, may be combinedwith one or more support materials or carriers using one of the supportmethods well known in the art or as described below. For example, in amost preferred embodiment, a bulky ligand metallocene catalyst compoundor catalyst system is in a supported form, for example deposited on,contacted with, vaporized with, bonded to, or incorporated within,adsorbed or absorbed in, or on, a support or carrier.

The terms “support” or “carrier” are used interchangeably and are anysupport material, preferably a porous support material, includinginorganic or organic support materials. Non-limiting examples ofinorganic support materials include inorganic oxides and inorganicchlorides. Other carriers include resinous support materials such aspolystyrene, functionalized or crosslinked organic supports, such aspolystyrene divinyl benzene polyolefins or polymeric compounds, or anyother organic or inorganic support material and the like, or mixturesthereof.

The preferred carriers are inorganic oxides that include those Group 2,3, 4, 5, 13 or 14 metal oxides. The preferred supports include silica,alumina, silica-alumina and mixtures thereof. Other useful supportsinclude magnesia, titania, zirconia, magnesium chloride, montmorillonite(EP-B1 0 511 665), phyllosilicate, zeolites, talc, clays and the like.Also, combinations of these support materials may be used, for example,silica-chromium, silica-alumina, silica-titania and the like. Additionalsupport materials may include those porous acrylic polymers described inEP 0 767 184 B1, which is incorporated herein by reference. Othersupport materials include nanocomposites as described in PCT WO99/47598, which is herein incorporated by reference.

It is preferred that the carrier, most preferably an inorganic oxide,has a surface area in the range of from about 10 to about 700 m²/g, porevolume in the range of from about 0.1 to about 4.0 cc/g and averageparticle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the carrier is in the range of fromabout 50 to about 500 m²/g, pore volume of from about 0.5 to about 3.5cc/g and average particle size of from about 10 to about 200 μm. Mostpreferably the surface area of the carrier is in the range is from about100 to about 1000 m²/g, pore volume from about 0.8 to about 5.0 cc/g andaverage particle size is from about 5 to about 100 μm. The average poresize of the carrier of the invention typically has pore size in therange of from 10 to 1000 Å, preferably 50 to about 500 Å, and mostpreferably 75 to about 450 Å.

Examples of supporting bulky ligand metallocene catalyst systems aredescribed in U.S. Pat. Nos. 4,701,432, 4,808,561, 4,912,075, 4,925,821,4,937,217, 5,008,228, 5,238,892, 5,240,894, 5,332,706, 5,346,925,5,422,325, 5,466,649, 5,466,766, 5,468,702, 5,529,965, 5,554,704,5,629,253, 5,639,835, 5,625,015, 5,643,847, 5,665,665, 5,698,487,5,714,424, 5,723,400, 5,723,402, 5,731,261, 5,759,940, 5,767,032,5,770,664, 5,846,895 and 5,939,348 and U.S. application Ser. No. 271,598filed Jul. 7, 1994 and Ser. No. 788,736 filed Jan. 23, 1997 and PCTpublications WO 95/32995, WO 95/14044, WO 96/06187 and WO 97/02297, andEP-B1-0 685 494 all of which are herein fully incorporated by reference.

The method for making the catalyst composition generally involves thecombining, contacting, blending, and/or mixing of a catalyst system orpolymerization catalyst with a carboxylate metal salt, wherein thecatalyst system or polymerization catalyst is heated to a temperaturegreater than room temperature (25° C.), and then, contacted with thecarboxylate metal salt. In another embodiment, the temperature isgreater than 30 C, preferably greater than 40° C., more preferablygreater than 50° C., even more preferably greater than 60° C., and mostpreferably greater than 70° C.

In one embodiment of the method of the invention, a conventional-typetransition metal catalyst and/or a bulky ligand metallocene catalyst iscombined, contacted, blended, and/or mixed with at least one carboxylatemetal salt, wherein the catalyst is pre-heated to a temperature greaterthan 30° C., more preferably greater than 50° C., even more preferablygreater than 60° C., and most preferably greater than 70° C. In almostpreferred embodiment, the conventional-type transition metal catalystand/or the bulky ligand metallocene catalyst are supported on a carrier.

In another embodiment, the steps of the method of the invention includeforming a polymerization catalyst, preferably forming a supportedpolymerization catalyst, heating the polymerization catalyst or thesupported polymerization catalyst, and then contacting thepolymerization catalyst or supported polymerization catalyst with acarboxylate metal salt. In a preferred method, the polymerizationcatalyst comprises a catalyst compound, an activator or cocatalyst and acarrier, preferably the polymerization catalyst is a supported bulkyligand metallocene catalyst.

In one embodiment of the method of the invention the carboxylate metalsalt is contacted with the catalyst system, preferably a supportedcatalyst system, most preferably a supported bulky ligand metallocenecatalyst system, wherein the catalyst system is at a temperature in therange of from 30° C. to about 200° C., preferably from 40° C. to about150° C., more preferably from about 50° C. to about 120° C., and mostpreferably from about 60° C. to about 100° C.

In a preferred embodiment, the contacting of the heated polymerizationcatalyst or catalyst system (above room temperature) with a carboxylatemetal salt is performed under an inert gaseous atmosphere, such asnitrogen. However, it is contemplated that the combination of the heatedpolymerization catalyst and the carboxylate metal salt may be performedin the presence of olefin(s), solvents, hydrogen and the like.

In one embodiment of the method of the invention, the heatedpolymerization catalyst or catalyst system and the carboxylate metalsalt is combined in the presence of a liquid, for example the liquid maybe a mineral oil, toluene, hexane, isobutane or a mixture thereof. In amore preferred method a carboxylate metal salt is combined with a heatedpolymerization catalyst that has been formed in a liquid, preferably ina slurry, or combined with a substantially dry or dried, polymerizationcatalyst that has been placed in a liquid and reslurried.

In an embodiment, the contact time for the carboxylate metal salt andthe heated polymerization catalyst may vary depending on one or more ofthe conditions, temperature and pressure, the type of mixing apparatus,the quantities of the components to be combined, and even the mechanismfor introducing the polymerization catalyst/carboxylate metal saltcombination into the reactor.

Preferably, a heated polymerization catalyst, preferably a heated bulkyligand metallocene catalyst compound and a carrier, is contacted with acarboxylate metal salt for a period of time from about a second to about24 hours, preferably from about 1 minute to about 12 hours, morepreferably from about 10 minutes to about 10 hours, and most preferablyfrom about 30 minutes to about 8 hours.

Preferably, a heated polymerization catalyst, preferably a heated bulkyligand metallocene catalyst compound, the activator and the carrier, arecontacted with a carboxylate metal salt for a period of time from abouta second to about 24 hours, preferably from about 1 minute to about 12hours, more preferably from about 10 minutes to about 10 hours, and mostpreferably from about 30 minutes to about 8 hours.

In an embodiment, the ratio of the weight of the carboxylate metal saltto the weight of the transition metal of the catalyst compound is in therange of from about 0.01 to about 1000, preferably in the range of from1 to about 100, more preferably in the range of from about 2 to about50, and most preferably in the range of from 4 to about 20. In oneembodiment, the ratio of the weight of the carboxylate metal salt to theweight of the transition metal of the catalyst compound is in the rangeof from about 2 to about 20, more preferably in the range of from about2 to about 12, and most preferably in the range of from 4 to about 10.

In another embodiment of the method of the invention, the weight percentof the carboxylate metal salt based on the total weight of thepolymerization catalyst is in the range of from about 0.5 weight percentto about 50 weight percent, preferably in the range of from 1 weightpercent to about 25 weight percent, more preferably in the range of fromabout 2 weight percent to about 12 weight percent, and most preferablyin the range of from about 2 weight percent to about 10 weight percent.In another embodiment, the weight percent of the carboxylate metal saltbased on the total weight of the polymerization catalyst is in the rangeof from 1 to about 50 weight percent, preferably in the range of from 2weight percent to about 30 weight percent, and most preferably in therange of from about 2 weight percent to about 20 weight percent.

If the polymerization catalyst includes a carrier, the total weight ofthe polymerization catalyst includes the weight of the carrier.

It is preferred that for densities lower than 0.910 g/cc morecarboxylate metal salt is combined with the heated polymerizationcatalyst.

It is believed that the more metal of the activator, for example totalaluminum content or free aluminum content (the alkyl aluminum content inalumoxane), present in the polymerization catalyst, the more carboxylatemetal salt is required. Manipulating the amounts or loadings of thepolymerization catalyst components, i.e. the free aluminum may provide ameans for adjusting the level of carboxylate metal salt.

Mixing techniques and equipment contemplated for use in the method ofthe invention are well known. Mixing techniques may involve anymechanical mixing means, for example shaking, stirring, tumbling, androlling. Another technique contemplated involves the use offluidization, for example in a fluid bed reactor vessel where circulatedgases provide the mixing. Non-limiting examples of mixing equipmentinclude a ribbon blender, a static mixer, a double cone blender, a drumtumbler, a drum roller, a dehydrator, a fluidized bed, a helical mixerand a conical screw mixer.

In a preferred embodiment of the invention the catalyst system of theinvention is supported on a carrier, preferably the supported catalystsystem is substantially dried, preformed, substantially dry and/or freeflowing. In an especially preferred method of the invention, thepreformed supported catalyst system is heated to a temperature in therange of from 30° C. to 100° C. and contacted at around this temperaturewith a carboxylate metal salt. The carboxylate metal salt may be insolution or slurry or in a dry state, preferably the carboxylate metalsalt is in a substantially dry or dried state. In the most preferredembodiment, the carboxylate metal salt is contacted with a heatedsupported catalyst system, preferably a heated supported bulky ligandmetallocene catalyst system, in a rotary mixer under a nitrogenatmosphere, most preferably the mixer is a tumble mixer, or in afluidized bed mixing process, in which the polymerization catalyst andthe carboxylate metal salt are in a solid state, that is they are bothsubstantially in a dry state or in a dried state.

There are various other methods in the art for supporting apolymerization catalyst compound or catalyst system of the invention.For example, the bulky ligand metallocene catalyst compound may containa polymer bound ligand as described in U.S. Pat. Nos. 5,473,202 and5,770,755, which is herein fully incorporated by reference; the bulkyligand metallocene catalyst system may be spray dried as described inU.S. Pat. No. 5,648,310, which is herein fully incorporated byreference; the support used with the bulky ligand metallocene catalystsystem of the invention is functionalized as described in Europeanpublication EP-A-0 802 203, which is herein fully incorporated byreference, or at least one substituent or leaving group is selected asdescribed in U.S. Pat. No. 5,688,880, which is herein fully incorporatedby reference.

In a preferred embodiment, the invention provides for a supported bulkyligand metallocene catalyst system that includes a surface modifier thatis used in the preparation of the supported catalyst system as describedin PCT publication WO 96/11960, which is herein fully incorporated byreference. The catalyst systems of the invention can be prepared in thepresence of an olefin, for example hexene-1.

A preferred method for producing a supported bulky ligand metallocenecatalyst system is described below and is described in U.S. applicationSer. No. 265,533, filed Jun. 24, 1994 and Ser. No. 265,532, filed Jun.24, 1994 and PCT publications WO 96/00245 and WO 96/00243 both publishedJan. 4, 1996, all of which are herein fully incorporated by reference.In this preferred method, the bulky ligand metallocene catalyst compoundis slurried in a liquid to form a metallocene solution and a separatesolution is formed containing an activator and a liquid. The liquid maybe any compatible solvent or other liquid capable of forming a solutionor the like with the bulky ligand metallocene catalyst compounds and/oractivator of the invention. In the most preferred embodiment the liquidis a cyclic aliphatic or aromatic hydrocarbon, most preferably toluene.The bulky ligand metallocene catalyst compound and activator solutionsare mixed together heated and added to a porous support, optionally aheated porous support, or a porous support, optionally a heated poroussupport is added to the solutions such that the total volume of thebulky ligand metallocene catalyst compound solution and the activatorsolution or the bulky ligand metallocene catalyst compound and activatorsolution is less than four times the pore volume of the porous support,more preferably less than three times, even more preferably less thantwo times; preferred ranges being from 1.1 times to 3.5 times range andmost preferably in the 1.2 to 3 times range.

Procedures for measuring the total pore volume of a porous support arewell known in the art. Details of one of these procedures is discussedin Volume 1, Experimental Methods in Catalytic Research (Academic Press,1968) (specifically see pages 67-96). This preferred procedure involvesthe use of a classical BET apparatus for nitrogen absorption. Anothermethod well known in the art is described in Innes, Total Porosity andParticle Density of Fluid Catalysts By Liquid Titration, Vol. 28, No. 3,Analytical Chemistry 332-334 (March, 1956).

The mole ratio of the metal of the activator component to the metal ofthe supported bulky ligand metallocene catalyst compounds are in therange of between 0.3:1 to 1000:1, preferably 20:1 to 800:1, and mostpreferably 50:1 to 500:1. Where the activator is an ionizing activatorsuch as those based on the anion tetrakis(pentafluorophenyl)boron, themole ratio of the metal of the activator component to the metalcomponent of the bulky ligand metallocene catalyst is preferably in therange of between 0.3:1 to 3:1.

In one embodiment of the invention, olefin(s), preferably C₂ to C₃₀olefin(s) or alpha-olefin(s), preferably ethylene or propylene orcombinations thereof are prepolymerized in the presence of the a bulkyligand metallocene catalyst system of the invention prior to the mainpolymerization. The prepolymerization can be carried out batchwise orcontinuously in gas, solution or slurry phase including at elevatedpressures. The prepolymerization can take place with any olefin monomeror combination and/or in the presence of any molecular weightcontrolling agent such as hydrogen. For examples of prepolymerizationprocedures, see U.S. Pat. Nos. 4,748,221, 4,789,359, 4,923,833,4,921,825, 5,283,278 and 5,705,578 and European publication EP-B-0279863 and PCT Publication WO 97/44371 all of which are herein fullyincorporated by reference.

In an embodiment, the method of the invention provides for co-injectinginto a reactor, an unsupported polymerization catalyst that is firstheated to a temperature greater than room temperature, and then combinedwith a carboxylate metal. In one embodiment the polymerization catalystis used in an unsupported form, preferably in a liquid form such asdescribed in U.S. Pat. Nos. 5,317,036 and 5,693,727 and Europeanpublication EP-A-0 593 083, all of which are herein incorporated byreference. The heated polymerization catalyst in liquid form can be fedwith a carboxylate metal salt, as a solid or a liquid, to a reactorusing the injection methods described in PCT publication WO 97/46599,which is fully incorporated herein by reference.

In one embodiment, the supported catalyst system containing acarboxylate metal salt, preferably the supported bulky ligandmetallocene-type catalyst system containing a carboxlate metal salt havea average flow time less than 150 seconds, preferably less than 100seconds, more preferably less than 75 seconds, even more preferably lessthan 50 seconds, still even more preferably less than 40 seconds, andmost preferably less than 20 seconds.

Where a carboxylate metal salt and a heated unsupported bulky ligandmetallocene catalyst system combination is utilized, the mole ratio ofthe metal of the activator component to the metal of the bulky ligandmetallocene catalyst compound is in the range of between 0.3:1 to10,000:1, preferably 100:1 to 5000:1, and most preferably 500:1 to2000:1.

Polymerization Process

The supported catalyst systems and/or compositions of the inventiondescribed above are suitable for use in any prepolymerization and/orpolymerization process over a wide range of temperatures and pressures.The temperatures may be in the range of from −60° C. to about 280° C.,preferably from 50° C. to about 200° C., and the pressures employed maybe in the range from 1 atmosphere to about 500 atmospheres or higher.

Polymerization processes include solution, gas phase, slurry phase and ahigh pressure process or a combination thereof. Particularly preferredis a gas phase or slurry phase polymerization of one or more olefins atleast one of which is ethylene or propylene.

In one embodiment, the process of this invention is directed toward asolution, high pressure, slurry or gas phase polymerization process ofone or more olefin monomers having from 2 to 30 carbon atoms, preferably2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. Theinvention is particularly well suited to the polymerization of two ormore olefin monomers of ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and decene-1.

Other monomers useful in the process of the invention includeethylenically unsaturated monomers, diolefins having 4 to 18 carbonatoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers andcyclic olefins. Non-limiting monomers useful in the invention mayinclude norbornene, norbornadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbornene, dicyclopentadiene and cyclopentene.

In the most preferred embodiment of the process of the invention, acopolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one alpha-olefin having from 4 to 15 carbon atoms,preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8carbon atoms, is polymerized in a gas phase process. In anotherembodiment of the process of the invention, ethylene or propylene ispolymerized with at least two different comonomers, optionally one ofwhich may be a diene, to form a terpolymer.

In one embodiment, the invention is directed to a polymerizationprocess, particularly a gas phase or slurry phase process, forpolymerizing propylene alone or with one or more other monomersincluding ethylene, and/or other olefins having from 4 to 12 carbonatoms. Polypropylene polymers may be produced using the particularlybridged bulky ligand metallocene catalysts as described in U.S. Pat.Nos. 5,296,434 and 5,278,264, both of which are herein incorporated byreference.

Typically in a gas phase polymerization process a continuous cycle isemployed where in one part of the cycle of a reactor system, a cyclinggas stream, otherwise known as a recycle stream or fluidizing medium, isheated in the reactor by the heat of polymerization. This heat isremoved from the recycle composition in another part of the cycle by acooling system external to the reactor. Generally, in a gas fluidizedbed process for producing polymers, a gaseous stream containing one ormore monomers is continuously cycled through a fluidized bed in thepresence of a catalyst under reactive conditions. The gaseous stream iswithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product is withdrawn from the reactor and freshmonomer is added to replace the polymerized monomer. (See for exampleU.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749,5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228, allof which are fully incorporated herein by reference.)

The reactor pressure in a gas phase process may vary from about 100 psig(690 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferablyin the range of from about 250 psig (1724 kPa) to about 350 psig (2414kPa).

The reactor temperature in a gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C.

Other gas phase processes contemplated by the process of the inventioninclude series or multistage polymerization processes. Also gas phaseprocesses contemplated by the invention include those described in U.S.Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, and European publicationsEP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 and EP-B-634 421 all ofwhich are herein fully incorporated by reference.

In a preferred embodiment, the reactor utilized in the present inventionis capable and the process of the invention is producing greater than500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), evenmore preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still morepreferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even morepreferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferablygreater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr(45,500 Kg/hr).

A slurry polymerization process generally uses pressures in the range offrom about 1 to about 50 atmospheres and even greater and temperaturesin the range of 0° C. to about 120° C. In a slurry polymerization, asuspension of solid, particulate polymer is formed in a liquidpolymerization diluent medium to which ethylene and comonomers and oftenhydrogen along with catalyst are added. The suspension including diluentis intermittently or continuously removed from the reactor where thevolatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

A preferred polymerization technique of the invention is referred to asa particle form polymerization, or a slurry process where thetemperature is kept below the temperature at which the polymer goes intosolution. Such technique is well known in the art, and described in forinstance U.S. Pat. No. 3,248,179, which is fully incorporated herein byreference. Other slurry processes include those employing a loop reactorand those utilizing a plurality of stirred reactors in series, parallel,or combinations thereof. Non-limiting examples of slurry processesinclude continuous loop or stirred tank processes. Also, other examplesof slurry processes are described in U.S. Pat. No. 4,613,484, which isherein fully incorporated by reference.

In an embodiment the reactor used in the slurry process of the inventionis capable of and the process of the invention is producing greater than2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr(4540 Kg/hr). In another embodiment the slurry reactor used in theprocess of the invention is producing greater than 15,000 lbs of polymerper hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

Examples of solution processes are described in U.S. Pat. Nos.4,271,060, 5,001,205, 5,236,998 and 5,589,555 and PCT WO 99/32525, whichare fully incorporated herein by reference.

A preferred process of the invention is where the process, preferably aslurry or gas phase process is operated in the presence of a bulkyligand metallocene catalyst system of the invention and in the absenceof or essentially free of any scavengers, such as triethylaluminum,trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum anddiethyl aluminum chloride, dibutyl zinc and the like. This preferredprocess is described in PCT publication WO 96/08520 and U.S. Pat. Nos.5,712,352 and 5,763,543, which are herein fully incorporated byreference.

Polymer Products

The polymers produced by the process of the invention can be used in awide variety of products and end-use applications. The polymers producedby the process of the invention include linear low density polyethylene,elastomers, plastomers, high density polyethylenes, medium densitypolyethylenes, low density polyethylenes, polypropylene andpolypropylene copolymers.

The polymers, typically ethylene based polymers, have a density in therange of from 0.86 g/cc to 0.97 g/cc, preferably in the range of from0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900 g/ccto 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to0.940 g/cc, and most preferably greater than 0.915 g/cc, preferablygreater than 0.920 g/cc, and most preferably greater than 0.925 g/cc.Density is measured in accordance with ASTM-D-1238.

The polymers produced by the process of the invention typically have amolecular weight distribution, a weight average molecular weight tonumber average molecular weight (M_(w)/M_(n)) of greater than 1.5 toabout 15, particularly greater than 2 to about 10, more preferablygreater than about 2.2 to less than about 8, and most preferably from2.5 to 8.

Also, the polymers of the invention typically have a narrow compositiondistribution as measured by Composition Distribution Breadth Index(CDBI). Further details of determining the CDBI of a copolymer are knownto those skilled in the art. See, for example, PCT Patent Application WO93/03093, published Feb. 18, 1993, which is fully incorporated herein byreference.

The bulky ligand metallocene catalyzed polymers of the invention in oneembodiment have CDBI's generally in the range of greater than 50% to100%, preferably 99%, preferably in the range of 55% to 85%, and morepreferably 60% to 80%, even more preferably greater than 60%, still evenmore preferably greater than 65%.

In another embodiment, polymers produced using a bulky ligandmetallocene catalyst system of the invention have a CDBI less than 50%,more preferably less than 40%, and most preferably less than 30%.

The polymers of the present invention in one embodiment have a meltindex (MI) or (I₂) as measured by ASTM-D-1238-E in the range from 0.01dg/min to 1000 dg/min, more preferably from about 0.01 dg/min to about100 dg/min, even more preferably from about 0.1 dg/min to about 50dg/min, and most preferably from about 0.1 dg/min to about 10 dg/min.

The polymers of the invention in an embodiment have a melt index ratio(I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of from 10 to less than 25,more preferably from about 15 to less than 25.

The polymers of the invention in a preferred embodiment have a meltindex ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of frompreferably greater than 25, more preferably greater than 30, even morepreferably greater that 40, still even more preferably greater than 50and most preferably greater than 65. In an embodiment, the polymer ofthe invention may have a narrow molecular weight distribution and abroad composition distribution or vice-versa, and may be those polymersdescribed in U.S. Pat. No. 5,798,427 incorporated herein by reference.

In yet another embodiment, propylene based polymers are produced in theprocess of the invention. These polymers include atactic polypropylene,isotactic polypropylene, hemi-isotactic and syndiotactic polypropylene.Other propylene polymers include propylene block or impact copolymers.Propylene polymers of these types are well known in the art see forexample U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851, 5,036,034 and5,459,117, all of which are herein incorporated by reference.

The polymers of the invention may be blended and/or coextruded with anyother polymer. Non-limiting examples of other polymers include linearlow density polyethylenes produced via conventional Ziegler-Natta and/orbulky ligand metallocene catalysis, elastomers, plastomers, highpressure low density polyethylene, high density polyethylenes,polypropylenes and the like.

Polymers produced by the process of the invention and blends thereof areuseful in such forming operations as film, sheet, and fiber extrusionand co-extrusion as well as blow molding, injection molding and rotarymolding. Films include blown or cast films formed by coextrusion or bylamination useful as shrink film, cling film, stretch film, sealingfilms, oriented films, snack packaging, heavy duty bags, grocery sacks,baked and frozen food packaging, medical packaging, industrial liners,membranes, etc. in food-contact and non-food contact applications.Fibers include melt spinning, solution spinning and melt blown fiberoperations for use in woven or non-woven form to make filters, diaperfabrics, medical garments, geotextiles, etc. Extruded articles includemedical tubing, wire and cable coatings, pipe, geomembranes, and pondliners. Molded articles include single and multi-layered constructionsin the form of bottles, tanks, large hollow articles, rigid foodcontainers and toys, etc.

In order to provide a better understanding of the present inventionincluding representative advantages thereof, the following examples areoffered.

COMPARATIVE EXAMPLE 1

Witco Aluminum Stearate #22 (AlSt #22) [CH₃(CH₂)₁₆COO]₂Al—OH availablefrom Witco Corporation, Memphis, Tenn. was used. This is also thecarboxylate metal salt used in the examples below. The untapped bulkdensity, and sieve flow characteristics of this sample were measured andrecorded in Table 1.

EXAMPLE 2

Sieving Test Used for Measuring Flow Properties

The following procedure outlines the steps followed to measure catalystflowability using the ATM Sonic Sifter. The test was used to compare thevarious catalyst compositions by measuring the time it takes for a 2.0gram sample to pass through a selected sieve size. The preferred sievesize is 18 mesh or 1,000 microns. The sonic sifter was used as a tappingdevice only with the amplitude for sifting mechanism set to zero.Because the catalyst samples tested are air and moisture sensitive, itis necessary to perform the test under anaerobic conditions. The stepswere as follows:

1) Two grams of the catalyst sample to be measured is weighed intoplastic boat with pour spout.

2) The 18 mesh sieve is placed on the fines collection device and aplastic powder funnel with a 17 mm opening is placed on the top of thesieve.

3) The 2.0 gram catalyst sample is poured down the slope of the funnel.

4) The funnel is slowly lifted and the catalyst sample is allowed tospread out on the top of the sieve.

5) The five spacers are carefully placed above the 18 mesh screen andthe stack is locked together.

6) The assembly (screen and spacers) is placed inside of the testchamber of the sonic sifter.

7) The arms holding the stack together are unlocked so that the springsin the top of the assembly will operate freely.

8) The amplitude setting is checked to make sure it is set to zero. Thetapping function (one tap every 4 sec) only will be employed.

9) The stopwatch is started when the first tap is observed.

10) The stopwatch is stopped when the entire sample has passed throughthe sieve.

11) The sonic sifter timer is then turned off.

12) The stopwatch time is recorded in the lab notebook and the procedurerepeated.

EXAMPLE 3

Funnel Test Used for Measuring Flow Properties

The following procedure outlines the steps followed to measure catalystflowability using the funnel test. Because the catalyst samples testedare air and moisture sensitive, it is necessary to perform the testunder anaerobic conditions. The funnel sizes used are 14, 12, 10 and 5mm opening. The steps were as follows:

1) Twenty grams of the catalyst sample to be measured is weighed into 14mm funnel with bottom covered.

2) The stopwatch is started when the bottom cover is removed.

3) The stopwatch is stopped when the entire sample has passed through.

4) The stopwatch time is recorded in the lab notebook and the procedurerepeated using a smaller size funnel. If catalyst doesn't flow throughcertain size funnel, there are no further tests using smaller sizefunnel.

EXAMPLE 4

Preparation of a Supported Unbridged Bulky Ligand Metallocene CatalystSystem

Into a 2 gallon (7.57 liters) reactor was charged first with 2.0 litersof toluene then, 1060 g of 30 wt % methylalumoxane solution in toluene(available from Albemarle, Baton Rouge, La.), followed by 23.1 g ofbis(1,3-methyl-n-butyl cyclopentadienyl) zirconium dichloride as a 10%solution in toluene. The mixture was stirred for 60 minutes at roomtemperature after which 850 g of silica (Davison 948 dehydrated at 600°C. available from W. R. Grace, Davison Chemical Division, Baltimore,Md.) was added to the liquid with slow agitation. Stirring speed wasincreased for approximately 10 minutes to insure dispersion of thesilica into the liquid and then appropriate amount of toluene was addedto make up a slurry of liquid to solid having a consistency of 4 cc/g ofsilica. Mixing was continued for 15 minutes at 120 rpm after which 6 gof Kemamine AS-990 (available Witco Corporation, Memphis, Tenn.) wasdissolved in 100 cc of toluene and was added and stirred for 15 minutes.Drying was then initiated by vacuum and some nitrogen purge at 175° F.(79.4° C.). When the polymerization catalyst comprising the carrier,silica, appeared to be free flowing, it was cooled down and dischargedinto a nitrogen purged vessel. An approximate yield of 1 Kg of drypolymerization catalyst was obtained due to some loses due to drying.

COMPARATIVE EXAMPLE 5

Blending with Supported Catalyst System

Supported unbridged metallocene catalyst with good flowability wasblended as described above with 4 weight percent carboxylate metal saltat room temperature. 15 lb (6.8 kg) good flow supported catalyst wascharged to the 45L Jaygo Conical Screw Blender at room temperature. 0.6lb (0.273 kg) (4 wt %) carboxylate metal salt was then added on top ofthe supported catalyst. The blending was then started with 20 RPM screwspeed and 1 RPM auger speed. Samples were taken at 10, 15, and 30minutes from the bottom discharge line by stopping screw and auger.Samples were then tested for flowability using test described inExamples 2 and 3 (BS-4).

COMPARATIVE EXAMPLE 6

Blending with Supported Catalyst System

Example 6 is similar to Example 5 except that nitrogen bubbling wasused. 15 lb (6.8 kg) good flow supported catalyst was charged to the 45LJaygo Conical Screw Blender at room temperature. 0.6 lb (0.272 kg) (4 wt%) carboxylate metal salt was then added on top of the supportedcatalyst. A nitrogen flow was then started through the bottom dischargeline. Nitrogen flow was regulated to created some bubbling in thecatalyst bed. The blending was then started with 20 RPM screw speed and1 RPM auger speed. Samples were taken at 10, 15, and 30 minutes from thebottom discharge line by stopping screw and auger. Samples were thentested for flowability using test described in Examples 2 and 3 (BS-5).

EXAMPLE 7

Blending with Supported Catalyst System

Example 7 is similar to Example 5 except that 3 weight percent insteadof 4 weight percent carboxylate metal salt was used. 15 lb (6.8 kg) goodflow supported catalyst was charged to the 45L Jaygo Conical ScrewBlender at room temperature. 0.45 lb (0.204 kg) (3 wt %) carboxylatemetal salt was then added on top of the supported catalyst. The blendingwas then started with 20 RPM screw speed and 1 RPM auger speed. Sampleswere taken at 4, 15, and 30 minutes from the bottom discharge line bystopping screw and auger. Samples were then tested for flowability usingtest described in Examples 2 and 3 (BS-11A).

EXAMPLE 8

Blending with Supported Catalyst System

Example 8 is similar to Example 7 except that different batches ofcarboxylate metal salt and bare supported catalyst were used. 15 lb (6.8kg) good flow supported catalyst was charged to the 45L Jaygo ConicalScrew Blender at room temperature. 0.45 lb (0.204 kg) (3 wt %)carboxylate metal salt was then added on top of the supported catalyst.A nitrogen flow was then started through the bottom discharge line. Theblending was then started with 20 RPM screw speed and 1 RPM auger speed.Samples were taken at 4, 15, and 30 minutes from the bottom dischargeline by stopping screw and auger. Samples were then tested forflowability using test described in Examples 2 and 3 (BS-13).

EXAMPLE 9

Blending with Supported Catalyst System

Example 9 is a high temperature blending test with supported unbridgedmetallocene catalyst. The 45L Jaygo Conical Screw Blender was firstheated to 175° F. (79.4° C.) jacket temperature. 15 lb (6.8 kg) goodflow supported catalyst was then charged to the Jaygo Blender and washeated for 1 hour at 20 RPM screw speed and 1 RPM auger speed. After 1hour of heating, 0.60 lb (0.272 kg) (4 wt %) carboxylate metal salt wasthen added on top of the supported catalyst. The blending was thenstarted with 20 RPM screw speed and 1 RPM auger speed. Samples weretaken at 4 and 15 minutes from the bottom discharge line by stoppingscrew and auger. The screw was stopped after 15 minutes blending andblender content was statically heated up to 24 hours. Samples were takenat 4, 18 and 24 hours static heating to test the effects of staticheating on catalyst flowability. Samples were then tested forflowability using test described in Examples 2 and 3 (BS-18).

EXAMPLE 10

Blending with Supported Catalyst System

Example 10 is also a high temperature blending test similar to Example 9except that the total blending time was 30 minutes and there was nostatic heating after blending. The 45L Jaygo Conical Screw Blender wasfirst heated to 175° F. (79.4° C.) jacket temperature. 15 lb (6.8 kg)good flow supported catalyst was charged to the Jaygo Blender and washeat for 1 hour at 20 RPM screw speed and 1 RPM auger speed. After 1hour of heating, 0.60 lb (0.272 kg) (4 wt %) carboxylate metal salt wasthen added on top of the supported catalyst. The blending was thenstarted with 20 RPM screw speed and 1 RPM auger speed. Samples weretaken at 4, 15, and 30 minutes from the bottom discharge line bystopping screw and auger. Samples were then tested for flowability usingtest described in Examples 2 and 3 (BS-19).

EXAMPLE 11

Blending with Supported Catalyst System

Example 11 is also a high temperature blending test similar to Example 9except that a bridged supported metallocene catalyst was used. The 45LJaygo Conical Screw Blender was first heated to 175° F. (79.4° C.)jacket temperature. 15 lb (6.8 kg) good flow supported bridged catalystwas charged to the Jaygo Blender and was heated for 1 hour at 20 RPMscrew speed and 1 RPM auger speed. After 1 hour of heating, 0.60 lb(0.272 kg) (4 wt %) carboxylate metal salt was then added on top of thesupported catalyst. The blending was then started with 20 RPM screwspeed and 1 RPM auger speed. Samples were taken at 4, 15, and 30 minutesfrom the bottom discharge line by stopping screw and auger. Samples werethen tested for flowability using test described in Examples 2 and 3(BS-21).

TABLE 1 Flowability at 4% Carboxylate Metal Salt at Normal and HighTemperature Mixing Blending Time Flow- 14 mm 12 mm 10 mm 7 mm 5 mm sieveExamples Temp (min) ability (sec) (sec) (sec) (sec) (sec) (sec) CEX 5Room 10 Poor NF NF NF NF NF 94 15 Poor NF NF NF NF NF 90 30 Poor NF NFNF NF NF 142 CEX 6 Room  5 Poor NF NF NF NF NF 86 15 Poor NF NF NF NF NF88 30 Poor NF NF NF NF NF 110 EX 9 High  4 Good 2.0 5.0 9.0 NF NF 52(175° F.)  5 Good 2.0 5.0 12.0  NF NF 74 4 hr (heating) Good 3.3 4.010.5  NF NF 60 EX 10 High  4 Good 1.4 2.0 5.5 40.0 133.0 31 (175° F.) 15Good/Fair 4.0 5.2 13.5/NF NF NF 69 30 Fair 2.4 7.0/1T NF NF NF 76 EX 11High  4 Good 1.7 2.2 3.0 72.3 245(1T) (175° F.) 15 Good 1.5 2.5 5.0 NFNF  30a Good/Fair 2.4 7.7(1T) NF NF NF  30b Good/Fair 1.9 3.0 NF NF NFNF means no flow. Good: good flow catalyst, pass all three funnels (14,12, 10 mm) Fair: fair flow catalyst, pass one or two funnels (14, 12, 10mm) Poor: poor flow catalyst, fail all three funnels (14, 12, 10 mm)

TABLE 2 Flowability at 4% Carboxylate Metal Salt at High Temperature and3% Carboxylate Metal Salt Control Blending Time Flow- 14 mm 12 mm 10 mm7 mm 5 mm sieve Examples Temp (min) ability (sec) (sec) (sec) (sec)(sec) (sec) EX 7 Room  4 Good 3.0 4.0 10.0 NF NF 60 15 Fair 4.0 8.0 NFNF NF 82 30 Poor NF NF NF NF NF 138 EX 8 Room  4 Good 4.0 6.0 13.0 NF NF54 15 Fair/Poor 4.0 NF NF NF NF 67 30 Poor NF NF NF NF NF 115 EX 9 High 4 Good 2.0 5.0  9.0 NF NF 52 (175 F.) 15 Good 2.0 5.0 12.0 NF NF 74 4hr (static) Good 3.3 4.0 10.5 NF NF 60 EX 10 High  4 Good 1.4 2.0  5.540.0 133.0 31 (175 F.) 15 Good/Fair 4.0 5.2 13.5/NF NF NF 69  30a Fair2.4 7.0/1T NF NF NF 76  30b Poor NF NF NF NF NF 67 Good: good flowcatalyst, pass all three funnels (14, 12, 10 mm) Fair: fair flowcatalyst, pass one or two funnels (14, 12, 10 mm) Poor: poor flowcatalyst, fail all three funnels (14, 12, 10 mm)

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For example, it is contemplated that twoor more supported catalyst compositions of the invention can be used.For this reason, then, reference should be made solely to the appendedclaims for purposes of determining the true scope of the presentinvention.

We claim:
 1. A method for making a catalyst composition, the methodcomprising the steps of: (a) heating a polymerization catalyst to atemperature greater than 30° C. to form a heated polymerizationcatalyst; and (b) combining the heated polymerization catalyst with acarboxylate metal salt.
 2. The method of claim 1 wherein thepolymerization catalyst comprises a bulky ligand metallocene catalystcompound.
 3. The method of claim 1 wherein the carboxylate metal salt isrepresented by the formula: MQ_(X)(OOCR)_(y) where M is a metal from thePeriodic Table of Elements; Q is halogen, or hydroxy, alkyl, alkoxy,aryloxy, siloxy, silane or sulfonate group; R is a hydrocarbyl radicalhaving from 2 to 100 carbon atoms; x is an integer from 0 to 3; y is aninteger from 1 to 4; the sum of x and y is equal to the valence of themetal M; Q is halogen or a hydroxy group; and R is a hydrocarbyl radicalhaving from 4 to 24 carbon atoms.
 4. The method of claim 1 wherein thetemperature is greater than 50° C.
 5. The method of claim 1 wherein thetemperature is in the range of from 60° C. to 100° C.
 6. A continuousprocess for polymerizing olefin monomer(s) in a reactor underpolymerization conditions, the process comprising the steps of: (a)introducing olefin monomer(s) to the reactor; (b) heating apolymerization catalyst to a temperature greater than room temperature;(b) adding a carboxylate metal salt to the heated polymerizationcatalyst to form a catalyst composition; (c) introducing the catalystcomposition to the reactor; and (d) withdrawing a polymer product fromthe reactor.
 7. The process of claim 6 wherein in step (b) thetemperature is greater than 50 C.
 8. The process of claim 6 wherein theamount of carboxylate metal salt is greater than 3.5 weight percentbased on the total weight percent of the polymerization catalyst.
 9. Theprocess of claim 8 wherein the in step (b) the temperature is in therange of from 60° C. to 100° C.
 10. The process of claim 6 wherein thecarboxylate metal salt is stearate compound.
 11. The process of claim 10wherein the carboxylate salt is used in an amount equal to or greaterthan 4 weight percent based on the total weight of the polymerizationcatalyst.